CN111234266A - Preparation method of chitosan/polyvinyl alcohol hydrogel dressing - Google Patents
Preparation method of chitosan/polyvinyl alcohol hydrogel dressing Download PDFInfo
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- CN111234266A CN111234266A CN202010164693.3A CN202010164693A CN111234266A CN 111234266 A CN111234266 A CN 111234266A CN 202010164693 A CN202010164693 A CN 202010164693A CN 111234266 A CN111234266 A CN 111234266A
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 74
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 61
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 61
- 239000000017 hydrogel Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000010257 thawing Methods 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 230000005855 radiation Effects 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000005251 gamma ray Effects 0.000 claims description 3
- 231100000987 absorbed dose Toxicity 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 abstract description 7
- 230000001954 sterilising effect Effects 0.000 abstract description 3
- 239000003999 initiator Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 206010052428 Wound Diseases 0.000 description 9
- 208000027418 Wounds and injury Diseases 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000035876 healing Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
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- 230000003385 bacteriostatic effect Effects 0.000 description 2
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- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000023555 blood coagulation Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 239000005017 polysaccharide Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0052—Mixtures of macromolecular compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/008—Hydrogels or hydrocolloids
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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Abstract
The invention discloses a preparation method of a chitosan/polyvinyl alcohol hydrogel dressing, and belongs to the technical field of high polymer materials. The method comprises the following steps: (1) obtaining the chitosan/polyvinyl alcohol solution. (2) And (3) performing freeze thawing and irradiation treatment to obtain the chitosan/polyvinyl alcohol hydrogel dressing. The chitosan/polyvinyl alcohol hydrogel synthesized by the method can obviously improve the appearance and mechanical property of the hydrogel, and the dressing prepared by the method does not need a cross-linking agent and an initiator, completes the molding and sterilization of the hydrogel dressing at the same time, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a method for preparing a hydrogel dressing, in particular to a method for preparing a chitosan/polyvinyl alcohol hydrogel dressing.
Background
Chitosan (CS), a natural basic polysaccharide, has excellent biocompatibility; the molecular weight of the composite has better antibacterial and blood coagulation functions within a certain range, is suitable for local treatment of wound surfaces, has low price, and is one of ideal materials of wound dressings. At present, the chitosan hydrogel dressing is commonly prepared by a chemical method, a radiation method, a physical method and the like. The freeze-thaw method is the method for effectively preparing the polyvinyl alcohol hydrogel which is firstly reported by Peppas, the hydrogel prepared by the method has the advantages of good elasticity, high mechanical strength and the like, but the hydrogel is a physical gel, can be dissolved into a solution at a higher temperature, has small swelling degree and is opaque, and the observation of wounds in the treatment process is influenced. The Chinese patent publication No. CN1679972A, the publication date of 10.12.2005, the invention name "chitosan hydrogel burn dressing with gradient structure and preparation method thereof" discloses a preparation method of chitosan hydrogel burn dressing. The Chinese publication No. CN101502667B, the publication No. CN103480034A, the publication No. 2014 1/10, the invention name "radiation crosslinking chitosan/gelatin/polyvinyl alcohol hydrogel dressing and a preparation method and application thereof", the Chinese patent publication No. CN1579559, the publication No. 2005 2/16, the invention name "polyvinyl alcohol hydrogel dressing containing medicine and chitosan and a preparation method thereof", and the like disclose a case that natural polymer chitosan is compounded and synthesized into a polymer, and the hydrogel dressing is formed by using a radiation crosslinking method. The chitosan hydrogel dressing is successfully obtained by the technical method, but toxic reagents such as glyoxal, glutaraldehyde and the like are used as cross-linking agents, and even if trace residues of the toxic cross-linking agents exist, the toxic cross-linking agents still cause damage to human tissues to different degrees and affect the healing of wound surfaces; and the irradiation method can cause the problem that the chitosan in the chitosan hydrogel dressing is degraded greatly under the irradiation condition of high-energy rays, so that the hydrogel strength is poor. Therefore, what is needed is a simple method for synthesizing chitosan hydrogel while simultaneously solving the problems of mechanical properties and transparency, while avoiding the use of toxic cross-linking agents.
Disclosure of Invention
The invention aims to provide a preparation method of a chitosan/polyvinyl alcohol hydrogel dressing, which has good biocompatibility, no toxicity and simple preparation process. The method does not need a cross-linking agent and an initiator, can complete the forming and sterilization of the hydrogel dressing at the same time, and makes up the defects of synthesizing the hydrogel by a radiation method and a physical method.
In order to realize the purpose of the invention, the preparation method of the chitosan/polyvinyl alcohol hydrogel dressing comprises the following steps:
(1) first, a chitosan/polyvinyl alcohol solution is obtained.
(2) Then the chitosan/polyvinyl alcohol hydrogel dressing is obtained by irradiation treatment after the freeze thawing.
The method specifically comprises the following steps:
(1) dissolving chitosan powder in an acetic acid solution with the mass percentage of 1% to obtain a chitosan solution with the mass volume concentration of 1% -2%.
(2) Adding polyvinyl alcohol into distilled water to obtain a polyvinyl alcohol solution with the mass fraction of 8% -12%.
(3) And (3) mixing the two solutions obtained in the step (1) and the step (2) to obtain a chitosan/polyvinyl alcohol solution.
(4) And (4) defoaming the chitosan/polyvinyl alcohol solution obtained in the step (3) in vacuum, transferring the defoamed solution to a mold, and performing freeze-thawing treatment. Then proceed with60And (5) irradiating by Co gamma rays to obtain the chitosan/polyvinyl alcohol hydrogel dressing.
The molecular weight of the chitosan powder is preferably 1-10 ten thousand.
Stirring at 70-90 ℃ under the water bath condition is preferably selected in the step (2).
The volume ratio of the chitosan solution to the polyvinyl alcohol solution in the step (3) is preferably 1: 1 to 5.
The number of times of freezing and thawing in the step (4) is preferably 1-7 times.
Said step (4)60The dosage of Co gamma ray irradiation absorption is preferably 25-45 kGy.
The preparation method of the invention has the following advantages and beneficial effects:
(1) the preparation method of the invention adopts the technology of combining freeze thawing and radiation, fully exerts the synergistic effect of physical crosslinking and chemical crosslinking, and the prepared chitosan/polyvinyl alcohol hydrogel has good transparency and the swelling ratio of more than 187 percent.
(2) The preparation method adopts a freeze-thaw treatment mode, solves the problem of foaming of the chitosan/polyvinyl alcohol hydrogel by direct radiation, overcomes the defect of poor strength of the chitosan/polyvinyl alcohol hydrogel prepared by direct radiation, and endows the dressing with good mechanical property, tensile strength of 0.0268MPa and breaking elongation of 234.86%.
(3) The dressing prepared by the preparation method of the invention has double functions of crosslinking hydrogel and sterilizing.
(4) The preparation method of the invention does not add any toxic cross-linking agent such as aldehydes, and the prepared hydrogel has good biocompatibility, does not cause any damage to the wound surface, and is beneficial to the healing of the wound surface.
(5) The chitosan/polyvinyl alcohol hydrogel dressing prepared by the preparation method can absorb wound exudate, create a good healing environment for the wound and promote the rapid healing of the wound.
Drawings
FIG. 1 is an appearance of the chitosan/polyvinyl alcohol hydrogel obtained in example 1 and a control group, (a)30kGy irradiation method; (b) a freeze-thaw method; (c) example 1.
FIG. 2 is a graph showing the mechanical properties of the chitosan/polyvinyl alcohol hydrogel obtained in example 1 and a control group, (a)30kGy irradiation method; (b) a freeze-thaw method; (c) example 1.
FIG. 3 is a graph of the bacteriostatic properties of the hydrogel obtained in example 1, (a) (b) chitosan/polyvinyl alcohol hydrogel; (c) (d) polyvinyl alcohol hydrogel.
Detailed Description
The present invention will be described in further detail with reference to specific examples and drawings, but the embodiments of the present invention are not limited thereto.
In order to compare the improvement effect of the technical scheme of the invention on the performance of the hydrogel, the preparation processes of a radiation method and a freeze-thaw method are adopted for comparison under the condition of the same proportion of raw materials.
Freeze-thaw method (DR): freezing the chitosan/polyvinyl alcohol mixed solution sample at-20 ℃ for 24h, taking out and unfreezing for 24h at room temperature;
radiation method: placing the chitosan/polyvinyl alcohol mixed solution and the sample after vacuum defoaming into a radiation chamber for carrying out60Co gamma ray irradiation, and the absorbed dose is 30 kGy.
Example 1:
weighing chitosan powder with the relative molecular weight of 5w, placing the chitosan powder into acetic acid solution with the mass percentage content of 1%, and stirring the solution to form chitosan solution with the mass volume concentration of 1%. 10g of polyvinyl alcohol are weighed out and added to 90ml of distilled waterStirring for 3h at 85 ℃ until a clear and transparent polyvinyl alcohol solution with the mass fraction of 10% is formed. Mixing a chitosan solution and a polyvinyl alcohol solution according to a volume ratio of 1: 1, uniformly stirring after mixing, and standing for defoaming under a vacuum condition; then pouring the chitosan/polyvinyl alcohol mixed solution into a mould, carrying out freeze-thaw treatment for 2 times, and then carrying out60And (4) irradiating by Co gamma rays, wherein the radiation absorption dose is 30kGy, and obtaining the chitosan/polyvinyl alcohol hydrogel dressing.
The appearance diagram, the mechanical property diagram and the bacteriostatic property diagram of the chitosan/polyvinyl alcohol hydrogel dressing obtained in this example are respectively shown in fig. 1, fig. 2 and fig. 3.
The swelling ratio of the chitosan/polyvinyl alcohol hydrogel dressing obtained in this example was 187%.
Example 2:
weighing chitosan powder with the relative molecular weight of 5w, placing the chitosan powder into acetic acid solution with the mass percentage content of 1%, and stirring the solution to form chitosan solution with the mass volume concentration of 1%. 10g of polyvinyl alcohol is weighed, added to 90ml of distilled water and stirred for 3h at 85 ℃ until a clear and transparent polyvinyl alcohol solution with a mass fraction of 10% is formed. Mixing a chitosan solution and a polyvinyl alcohol solution according to a volume ratio of 1: 3, uniformly stirring after mixing, and standing for defoaming under a vacuum condition; then pouring the chitosan/polyvinyl alcohol mixed solution into a mould, carrying out freeze-thaw treatment for 1 time, and then carrying out60And (4) irradiating by Co gamma rays, wherein the radiation absorption dose is 30kGy, and obtaining the chitosan/polyvinyl alcohol hydrogel dressing.
The swelling ratio of the chitosan/polyvinyl alcohol hydrogel dressing obtained in this example was 153%.
Example 3:
weighing chitosan powder with the relative molecular weight of 1-2 w, placing the chitosan powder into an acetic acid solution with the mass percentage of 1%, and stirring the solution to form a chitosan solution with the mass volume concentration of 2%. 10g of polyvinyl alcohol is weighed, added to 90ml of distilled water and stirred for 3h at 85 ℃ until a clear and transparent polyvinyl alcohol solution with a mass fraction of 10% is formed. Mixing a chitosan solution and a polyvinyl alcohol solution according to a volume ratio of 1: 1, uniformly stirring after mixing, and standing for defoaming under a vacuum condition; then pouring the chitosan/polyvinyl alcohol mixed solution into the reactorIn the mold, after 2 times of freeze thawing treatment, the hydrogel strip mold is subjected to60And (4) irradiating by Co gamma rays, wherein the radiation absorption dose is 40kGy, and obtaining the chitosan/polyvinyl alcohol hydrogel dressing.
The swelling ratio of the chitosan/polyvinyl alcohol hydrogel dressing obtained in this example was 192%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. A preparation method of a chitosan/polyvinyl alcohol hydrogel dressing is characterized by comprising the following steps:
(1) dissolving chitosan powder in an acetic acid solution with the mass percentage of 1% to obtain a chitosan solution with the mass volume concentration of 1% -2%;
(2) adding polyvinyl alcohol into distilled water to obtain a polyvinyl alcohol solution with the mass fraction of 8% -12%;
(3) mixing the two solutions obtained in the step (1) and the step (2) to obtain a chitosan/polyvinyl alcohol solution;
(4) defoaming the chitosan/polyvinyl alcohol solution obtained in the step (3) in vacuum, transferring the defoamed chitosan/polyvinyl alcohol solution into a mold, and performing freeze thawing treatment; then proceed with60And (5) irradiating by Co gamma rays to obtain the chitosan/polyvinyl alcohol hydrogel dressing.
2. The method for preparing the chitosan/polyvinyl alcohol hydrogel dressing according to claim 1, wherein the molecular weight of the chitosan powder is 1-10 ten thousand.
3. The method for preparing a chitosan/polyvinyl alcohol hydrogel dressing according to claim 1, wherein the volume ratio of the chitosan solution to the polyvinyl alcohol solution in the step (3) is selected from 1: 1 to 5.
4. The method for preparing the chitosan/polyvinyl alcohol hydrogel dressing according to claim 1, wherein the number of times of freezing and thawing in the step (4) is selected from 1 to 7 times.
5. The method for preparing a chitosan/polyvinyl alcohol hydrogel dressing as claimed in any one of claims 1 to 4, wherein said step (4)60The radiation absorbed dose of Co gamma ray is 25-45 kGy.
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Cited By (7)
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| CN111944519A (en) * | 2020-08-14 | 2020-11-17 | 大连工业大学 | Method for preparing chemiluminescence hydrogel |
| CN112190754A (en) * | 2020-09-09 | 2021-01-08 | 兰州大学 | Hydrogel dressing for treating wound defects and preparation method and application thereof |
| CN112546282A (en) * | 2020-12-17 | 2021-03-26 | 中国人民解放军总医院第四医学中心 | Cationic polymer medical antibacterial dressing and preparation method thereof |
| CN114191604A (en) * | 2021-12-06 | 2022-03-18 | 广东金发科技有限公司 | Slow-release antibacterial microsphere hydrogel dressing and preparation method and application thereof |
| CN114213679A (en) * | 2021-12-31 | 2022-03-22 | 华南理工大学 | Algal polysaccharide-based hydrogel and preparation method and application thereof |
| CN115124738A (en) * | 2022-07-11 | 2022-09-30 | 西南交通大学 | Double-layer bionic drug-loaded hydrogel and preparation and application thereof |
| CN116173283A (en) * | 2023-02-02 | 2023-05-30 | 江苏恰瑞生物科技有限公司 | Chitosan-polyvinyl alcohol SOD enzyme hydrogel dressing |
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| WO2022032714A1 (en) * | 2020-08-14 | 2022-02-17 | 大连工业大学 | Method for preparing chemiluminescent hydrogel |
| CN112190754A (en) * | 2020-09-09 | 2021-01-08 | 兰州大学 | Hydrogel dressing for treating wound defects and preparation method and application thereof |
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| CN114191604A (en) * | 2021-12-06 | 2022-03-18 | 广东金发科技有限公司 | Slow-release antibacterial microsphere hydrogel dressing and preparation method and application thereof |
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| CN114213679A (en) * | 2021-12-31 | 2022-03-22 | 华南理工大学 | Algal polysaccharide-based hydrogel and preparation method and application thereof |
| CN115124738A (en) * | 2022-07-11 | 2022-09-30 | 西南交通大学 | Double-layer bionic drug-loaded hydrogel and preparation and application thereof |
| WO2024012190A1 (en) * | 2022-07-11 | 2024-01-18 | 西南交通大学 | Double-layer bionic drug-loaded hydrogel, and preparation and use thereof |
| CN116173283A (en) * | 2023-02-02 | 2023-05-30 | 江苏恰瑞生物科技有限公司 | Chitosan-polyvinyl alcohol SOD enzyme hydrogel dressing |
| CN116173283B (en) * | 2023-02-02 | 2024-02-27 | 江苏恰瑞生物科技有限公司 | Chitosan-polyvinyl alcohol SOD enzyme hydrogel dressing |
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